Insecticidal compositions containing cyclopropane carboxylic acid esters



United States Patent 6 Claims. (Cl. 167--33) This invention relates to insecticidal compositions containing novel cyclopropanecarboxylic acid esters. More particularly, it relates to novel cyclopropanecarboxylic acid esters having the general formula,

wherein X X X and X each means a member selected from the group consisting of hydrogen and halogen atoms, methyl, nitro, methoxy, and cyano radicals; Z is a member of oxygen and sulfur atoms; Y is a member of the group consisting of a direct linkage and alkylene residue having carbon number of 1 to 3; and R is a member selected from methyl and methoxycarbonyl radicals; to a process for preparing the same; and to insecticidal compositions containing the same.

It is one object of the invention to provide a novel group of cyclopropanecarboxylic acid esters, particularly of chrysanthemum carboxylic acid esters, which have strong insecticidal activities to house and agricultural insects with low toxicities to warm-blooded animals and plants, and which can be commercially produced in low cost. Still another object is to provide insecticidal composition containing such an ester. Other objects would be obvious from the following description.

As an insecticide utilizable with safety because of the harmlessness to Warm-blooded animals, pyrethrum extract has long been employed. Recently, allethrin which is an analog of the effective ingredients in pyrethrum extract, i.e. pyrethrin and cinerin, was synthesized and developed for insectical uses. These ingredients are surely valuable in their high insecticidal powers, especially in their rapid effect to insects, and in the character-istics of permitting no, or little, resistivity to insects. However, their uses are limited to some extent because of their complicated steps of the production and their great expense for the production.

The present inventors have made broad researches on the various cyclopropanecarboxylic acid esters, and have now found the present novel group of cyclopropanecarboxylic acid esters, which possess significant insecticidal power but are harmless to warm-blooded animals, and which can be prepared from easily available materials by a simple process with low prices. In other words, the present compounds are (thio)phthalimido(alkyl) esters of chrysanthemum carboxylic acids. Accordingly, it is a feature of the present invention that the characteristics of the present compounds resemble pyrethrin, oinerin and allethrin, even though the alcohol moieties of the former are extremely simple as compared to those of the latter and are composed of carbon, hydrogen, oxygen CH CH and nitrogen atoms, unlike the latter composed of carbon,

hydrogen and oxygen.

Patented August 23, 1966 "ice Thus, the present invention is to provide novel cyclopropanecarboxylic acid esters having the formula,

wherein X X X X Z, Y and R have the same meanings as identified above, and to provide a process for preparing such compounds, comprising esterifying a phthalirnide compound having the general formula,

wherein X X X X Z and Y have the same meaning as identified above, with a cyclopropanecarboxylic acid having the general formula,

CH HOOCOHCHOH=C R Cfig \CH3 wherein R has the same meaning as identified above, according to the general esterifying procedure.

The phthalimide compound employed in the present invention may be prepared from phthalic acid, phthalic anhydride, phthalimide, and their nucleus-substituted compounds according to the conventional procedures well-known to those skilled in the art.

The cyclopropanecarboxylic acid employed in the present invention is either chrystanthemum monocarboxylic acid (R being CH or pyrethric acid (R being COOCH a monomethyl ester of chrysanthemum dicarboxylic acid). They are the acidic moieties of pyrethrin, cinerin and allethrin, and can be synthesized according to the known method.

The esterification reaction of the present invention may be eliected in various ways. The phthalimide compound may be heated with the cyclopropanecarboxylic acid in the presence of a strong acid, such as aromatic sulfonic acid and sulfuric acid, in an organic solvent capable of azeotropically boiling with water, thereby to remove the water formed in the esterification, out of the reaction system. It 'may also be heated with a lower alkyl ester of the cyclopropanecarboxylic acid in the presence of a basic catalyst, such as sodium and potassium, thereby to continuously remove the lower alcohol formed through the ester-exchanging reaction out of the reaction system. In such case, methyl, ethyl, n-propyl and isopropyl ester are suitable. In the most preferable esterification, it may be treated with the cyclopropanecarboxylic acid halide in an inert organic solvent, preferably in the presence of a de-hydrogen halide agent, whereby the esterification is proceeded with the isolation of a hydrohalic acid salt within a short period of time. In this case, the acid chloride is the most preferable, though the bromide and the iodide 'may be employable. Further, it may be refluxed with the cyclopropanecarboxylic acid anhydride in an inert solvent for several hours, thereby to yield the objective ester and free cyclopropanecarboxylic acid, the latter being recovered and again converted to the anhydride by treatment with, for example, acetic anhydride for reuse. Alternatively the phthalimide compound may be employed for the esterification in the form of the halide having the genral formula,

wherein X X X X Z and Y have the same meanings as identified above, and A 'means a halogen atom. In this case, the halide may be heated with an alkali metal salt of the cyclopropanecarboxylic acid in an inert solvent, thereby to yield the objective ester with the isolation of an alkali metal halide salt. In the formula, A may be any of chlorine, bromine, and iodine, among which the former two are preferable and practical. As the alkali metals, sodium and potassium are preferable.

As well-known, the cyclopropanecarboxylic acid as identified above comprises various stereoisomers and optical isomers. It is needless to say that the acid and the derivatives thereof as described herein involve their isomers.

The process of the invention is described in more detail with reference to the following examples, which are however to be construed for the purpose of illustration and not of the limitation.

Example 1 To a mixture of 17.7 g. (0.1 mole) of N-hydroxymethylphthalimide, 18 g. of Chrysanthemum monocarboxylic acid and 100 ml. of dry benzene, is added 1 g. of p-toluenesulfonic acid. The mixture is refluxed to remove the resulting water azeotropically. When the theoretical amount of water for the esterification is distilled oil, the mixture is cooled and washed with an aqueous saturated sodium bicarbonate solution to remove the acidic substance, and then with an aqueous saturated sodium chloride solution. The mixture is then distilled to remove the solvent. The residue is solidified, which is recrystallized from ligroin, thereby to yield phthalimidomethyl ester of chrystanthemum monocarboxylic acid, colorless scales, having M.P. 110-113 C., in yield of 26.2 g. (80%).

C3 CH3 Analysis.Found: C, 69.72; H, 6.50; N, 4.24%. Calculated (for C H NO C, 69.70; H, 6.47; N, 4.28%.

Example 2 A mixture of 17.7 g. (0.1 mole) of N-hydroxy-methylphthalimide and 19.6 g. of ethyl chrysanthemum monooarboxylate is heated at about 150 C., and 0.3 g. of sodium is added to the heated mixture, whereby ethyl alcohol starts to be distilled out. When the distilling is completed, 0.3 g. of sodium is added again thereto. The addition is repeated 7 times in total, whereby the theoretical amount of ethyl alcohol [for the esterification is distilled ofi. The mixture is then cooled, mixed with ethyl ether, washed with hydrochloric acid, with an :aqueous saturated sodium bicarbonate solution and then with a saturated sodium chloride solution, and dried over anhydrous sodium sulfate. Removal of the solvent from the mixture leaves 19.6 g. (60%) of phthalimidomethyl ester of chrysanthemum monocarboxylic acid.

4 Example 3 A mixture of 17.7 g. (0.1 mole) of N-hydroxymethylphthalimide, 50 ml. of dry toluene and 50 g. of pyridine, is cooled with ice, and a solution of 19 g. (1.02 moles) of Chrysanthemum monooarboxylic acid chloride dissolved in 50 ml. of toluene is added to the mixture. Upon the addition, pyridinium hydrochloride salt is isolated. After stirring at room temperature for 7 hours, the mixture is filtered, and the filtrate is washed with a dilute hydrochloric acid solution to remove excess of pyridine, then washed with a aqueous 5% sodium carbonate solution and with an aqueous saturated sodium chloride, subsequently. Upon distillation of toluene from the mixture in vacuo, crystals of phthalimidomethyl ester of Chrysanthemum monocarboxylic acid is obtained, which has M.P. 110113 C. after a recrystallization from toluene. The yield is 27.8 g.

Example 4 A mixture of 17.7 g. (0.1 mole) of N-hydroxymethylphthalimide, 32 g. of. chrysanthemum monocarboxylic acid anhydride and 60 g. of dry xylene, is refluxed for 3 hours. The mixture is then cooled and washed with an aqueous 3% sodium hydroxide solution at a temperature below 20 C., thereby to remove the lay-produced chrysanthemum monocarboxylic acid. The mixture is further washed with a saturated sodium chloride solution to remove alkaline substance, and then evaporated to remove xylene. Crystals of phthalimidomethyl ester of chrysanthemum monocarboxylic acid is obtained in 26.8 g. (81%) yield, which have M.P. l08112 C.

Example 5 A dispersion of 19 g. (0.1 mole) of sodium chrysanthemum monocarboxylate in a naphtha solvent is heated at about 150 C., and 20 g. of N-(chloromethyl)-phthalimide is added thereto over about 30 minutes. Esterification is proceeded with isolation of sodium chloride. Removal of the solvent by distillation in vacuo leaves 21.2 g. (65%) of phthalimidomethyl ester of chrysanthemum monocarboxylic acid.

Example 6 A mixture of 21.2 g. (0.1 mole) of 4-chloro-N-hydroxymethylphthalimide, 60 g. of pyridine and 50 ml. of dry toluene is treated with chrysanthemum monoc-arboxylic acid chloride as in Example 3, and 34.4 g. of 4-chlorophth alimidomethyl ester of chrysanthemum monocarboxylic acid is obtained. A recrystallization from ligroin yields colorless needles, M.P. 7983 C.

Cl CH3 CH CH Amzlysis.Found: C, 6280,11, 5.79; N, 3.88%. Cal- CH3 CH3 Analysis-Found: C, 56.23; H, 5.03; Br, 19.81%. Calculated (for C H NO Br): C, 56.17; H, 4.96;, Br, 19.67%.

Example 8 A mixture of 24.6 g. (0.1 mole) of 3,6-dichloro-N-hydroxymethylphthalimide, 60 g. of pyridine and 50 ml. of dry toluene, is treated with chrysanthemum monocarboxylic acid chloride as in Example 3, and 36.0 g. (91%) of 3,6-dichlorophthalimidornethyl ester of chrysanthemum monocarboxylic acid is obtained. A recrystallization from ligroin yields colorless needles, M.P. 120127 C.

Example 9 Using 31.5 g. (0.1 mole) of 3,4,5,6-tetrachloro-N-hy droxymethylphthalimide and 19 g. of chrysanthemum monocarboxylic acid chloride, the same procedure as in Example 3 is conducted, and 43.3 g. (93%) of 3,4,5,6- tetrachlorophthalimidomethyl ester of chrysanthemum monocarboxylic acid is obtained.

| CO OH 01 3 Analysia-Found: C, 49.11; H, 3.59; C], 30.66%. Calculated (for C H C1 NO c, 49.06; H, 3.63; 01, 30.49%.

Example Using 23.2 g. (0.1 mole) of 3-nitro-N-hydroxy-methylphthalimide and 19 g. of chrysanthemum monocarboxylic acid chloride, the same procedure as in Example 3 is conducted, and 32.7 g. (88%) of 3-nitrophthalirnidomethyl ester of chrysanthemum monocarboxylic acid is obtained. A recrystallization from a mixed ligroin-t-oluene solvent yields colorless needles, M.P. 118-120 C.

Analysia-Found: C, 61.35; H, 5.22; N, 7.55%. Ca1- culated (for clgHzoNgos): C, 61.29; H, 5.38; N, 7.53%.

Example 1 1 Using 23.0 g. (0.1 mole) of 4-nitro-N-hydroxyrnethylphthalirnide and 19 g. of chrysanthemum monocarboxylic acid chloride, the same procedure as in Example 3 is conducted, and 35.0 g. (90%) of 4-nitrophthalimidomethyl ester of chrysanthemum monocarboxylic acid is obtained. A recrystallization from a mixed ligroin-toluene solvent yields colorless needles, M.P. 125-130 C.

/CH; N-CH2OCCHOHOH=C OZN ll CH3 CH3 Analysis.Found: C, 61.40; H, 6.06; N, 7.50%. Calculated (for C I-1 N 0 C, 61.29; H, 5.38; N, 7.53%.

6 Example 12 Using 30.1 g. (0.1 mole) of 3-bromo-6-nitr0-N-hydroxymethylphthalirnide and 19 g. of chrysanthemum monocarboxylic acid chloride, the same esterification as in Example 3 is conducted, and 40.6 g. (90.0%) of yellow oily 3-bromo-6-nitrophthalimidomethyl ester of chrysanthemum monocarboxylic acid is obtained.

0 C CH 3 1 3r CH3 Analysis.Found: C, 50.83; H, 4.44; Br, 17.94%. Calculated (for C H BrN O C, 50.57;H, 4.24; Br, 17.71%.

Example 13 Using 19.1 g. (0.1 mole) of Sanethyl-N-hydroxy-methylphthalimide and 19 g. of chrysanthemum monocarbo'xylic acid chloride, the same esterification as in Example 3 is conducted, and 32.7 g. (96%) of oily 3-methylphthalimidomethyl ester of chrysanthemum monocarboxylic acid is obtained.

Analysis.Found: C, 70.50; H, 6.69; N, 4.35%. Calculated (for C H NO C, 70.36; H, 6.79; N, 4.10%.

Example 14 Using 19.1 g. (0.1 mole) of 4-methyl-N-hydroxymethylphthalirnide and 19 g. of chrysanthemum monocarboxylic acid chloride, the same esterification as in Example 3 is conducted, and 32.4 g. of oily 4-methylphthalirnidornethyl ester of chrysanthemum monocarboxylic acid is obtained.

CH CH3 Analysis.Found: C, 70.90; H, 6.58; N, 4.01%. Ca1- culated (for C H NO C, 70.36; H, 6.79; N, 4.10%.

Example 15 Using 20.7 g. (0.1 mole) of 4-methoxy-N-hydroxymethylphthalimide and 19 g. of chrysanthemum monocarboxylic acid chloride, the same esterification as in Example 3 is conducted, and 33.2 g. (93%) of pale yellow oily 4-methoxyphthalimidomethyl ester of chrysanthemum monocarboxylic acid is obtained.

C aO 0 H3 CH3 CH3 Analysis.Found: C, 68.00; H, 6.52; N, 4.10%. Calculated (for C H NO C, 67.21; H, 6.49; N, 3.92%.

Example 16 Using 24.2 g. of 3-chloro-4-methoxy-N-hydroxymethylphthalimide and 19 g. of chrysanthemum mono-carboxylic acid chloride, the same esterification as in Example 3 is conducted, and 37.6 g. (96%) of pale yellow oily 3- chloro-4-methoxyphthalimidomethyl ester of chrysanthcmum monocarboxylic acid is obtained.

culated (for C H ClNO C, 61.30; H, 5.66; CI, 9.05%.

Example 17 Using 20.2 g. (0.1 mole) of 4-cyano-N-hydroxy-methylphthalimide and 19 g. of chrysanthemum. monoca-rboxylic acid chloride, the same esterification as in Example 3 is conducted, and 33.1 g. (94%) of pale yellow only 4-cyanophthalimidomethyl ester of crysanthemum monocarboxylic acid is obtained.

NC CH O0 CH3 CH3 Analysis.Found: C, 68.01; H, 5.48; N, 8.10%. Calculated (for C2gH2 N204)I C, H, N, 7.95%.

Example 18 Using 17.7 g. (0.1 mole) of N-hydroxymethylphthalimide and 23.5 g. (0.102 mole) of pyrethryl chloride, the same esterification as in Example 3 is conducted, and 33.0 g. (89%) of pale yellow oily phthalimidomethyl ester of pyrethric acid is obtained.

\ COOCH;

CH3 CH3 Analysis.Found: C, 64.60; H, 5.73; N, 3.99%. Calculated (for C H NO )2 C, 64.68; H, 5.70; N, 3.77%.

Example 19 A mixture of 19.1 g. (0.1 mole) of N-(fi-hydroxyethyl) phthalimide, 60 g. of pyridine and 50 ml. of toluene, is cooled with ice, and a solution of 19 g. of Chrysanthemum monocar'boxylic acid chloride in 50 ml. of toluene is added thereto. The mixture is treated as in Example 3, and 30.7 g. (90%) of fi-(phthalimido)ethyl ester of chrysanthemum monocarboxylic acid is obtained. A recrystallization from ligroin yields crystals having M.P. 6568 C.

CO C 5 0&3 \CH3 Analysis.Found: C, 70.33; H, 6.87; N, 4.17%. Calculated (for C H NO C, 70.36; H, 6.79; N, 4.10%.

Example 20 C 0 CH3 C 3 8 Analysis-Pound: C; 70.90; H, 7.18; N, 3.74%. Calculated (for C H NO C, 70.96; H, 7.09; N, 3.94%.

Example 21 A mixture of 16.3 g. (0.1 mole) of N-hydroxy-phthalimide, 50 g. of pyridine and 40 m1. of dry toluene, is treated with chrysanthemum monocarboxylic acid chloride as in Example 3, and 30.0 g. (96.0%) of phthalimide ester (anhydri-de) of chrysanthemum monocarboxylic acid is obtained. A recrystallization from ligroin yields colorless needles, M.P. 70-75 C.

CH3 CH3 Analysis.Found: C, 69.03; H, 6.25; N, 4.41%. Calculated (for C H NO C, 68.99; H, 6.11; N, 4.47%.

Example 22 Using 19.3 g. (0.1 mole) of N-hydr-oxymethylthiophthalimide and 19 g. of chrysanthemum monocarboxylic acid chloride, the same esterification is conducted, and 32.0 g. (93%) of pink crystalline thiophthalimidomethyl ester of chrysanthemum monocarboxylic acid is obtained.

/CH3 NCH2OCCHOHCH=G CH3 CH Analysis.Found: C, 66.28; H, 6.09; S, 9.47%. Calculated (for C H NO S): C, 66.44; H, 6.16; S, 9.34%.

As mentioned above, the present esters possess superior insecticidal power, and exhibit rapid knock down and excellent killing efl'ect to house flies, mosquitos, cockroaches, etc. Moreover, these esters are especially useful for sanitary and domestic purpoes, because of their rapid efiectiveness and harmlessness (for example, phthalimidomethyl ester of chrysanthemum monocarboxylic acid shows oral toxicity to mice in LD value of more than 10 g./kg.). The present esters are suitably employed for the preparation of insecticidal compositions which have broad uses, correlatively with the low cost.

For the formulation of the insecticidal composition containing the present compound as the essential ingredient, oil solution, emulsifiable concentrate, wettable powder, dust, aerosol, mosquito coil, bait and other preparation, may be formulated using generally employed carrier, diluen-ts or auxiliary agents, according to the method known to those skilled in the art in the cases of the formulation of pyrethrum extract and allethrin. If the'compound is crystalline, it is preferably employed as a preliminarily prepared solution in an organic solvent, such as acetone, xylene, methylnaphthalene, etc., depending upon the type of the formulation.

If desired, the present esters may be employed for the preparation of the insecticidal compositions in combination with other insecticidal component, such as pyrethroide, for example, pyrethrum extract and allethrin, organochlorine and organophosphorus compounds, synergistic agent for pyrethroide, for example, piperonyl butoxide, sulfoxide, and the like. By combination with such other ingredient, the present insecticidal composition can be adapted to broader uses with more increased efiect.

Concretely speaking, the present esters may be blended with at least one of pyrethrin, allethrin, 0,0-dimethyl O-(3-methyl-4-nitrophenyl) thiophosphate, malathion, diazinone, dimethoate, 'y-BHC, and others, to yield a pesticidal composition which possesses high insecticidal activity with rapid efiectivity. In such cases, both components may be blended in a broad range of proportions, for example, in ratio of 0.05:1 to 120.05 by Weight of the ester to another insecticidal component.

The following are the illustrations of the insecticidal compositions containing the cyclopropanecarboxylic acid esters according to the invention and of the insecticidal activities.

Example 23 Each 0.4 gram of phthalimidomethyl ester (I), or monothiophthalimidomethyl ester (11), of chrysanthemum monocarboxylic acid was dissolved in 3 ml. of methylnaphthalene and a refined kerosene was added to the solution to make 100 ml., thereby to yield 0.3% oil solution.

In a glass box of 70 cm. cube about 30 house flies (adult) were liberated, and 0.3 ml. of the thus-prepared oil solution was uniformly sprayed with an atomizer into the box. Knock-down number of house flies according to the lapse of time were observed. Similarly, a 0.4% oil solution prepared using allethrin was tested for comparison.

10 Example 25 85 g. of Xylene and g. of Sorpol 2379 (a mixture of polyoxyethylene alkyl phenyl ether and alkyl aryl calcium sulfonate) were mixed with g. of 4-methylphthalimidomethyl ester (V) or 3-chloro-4-methoxyphthalimidomethyl ester (VI) of chrysanthemum monocarboxylic acid. Thus, a homogenous emulsifiable concentrate was obtained.

10 ml. of a solution obtained by dilution of the resulting 10% emulsifiable concentrate was sprayed onto houseflies (adult) in a settling-tower. After 5 -seconds, the shutter was opened and the houseflies were exposed to the sprayed air for 10 minutes and were then taken out from the settling-tower. The houseflies were kept in Knock-down ratio of houseflies according to the lapse of time, percent 30 42 1 1 min., 2 2 min, 4 5 min., 8

sec. sec. min. 25 sec min. 50 sec. min. 40 sec. min.

The compound (1) 5.4 .0 33.5 44.1 50.4 56.2 61.8 64.5 68.0 The compound (II) 3.8 14.0 33.1 40.0 50.3 57.3 62.0 68.0 68.3 Allethrin 1 7 .8 15 .7 27 .2 37 .9 48 .4 55 .8 56 .3 67 .1 69 .2

1 0.4% oil solution.

On the other hand, by use of the same equipment as above, a test was made by using common mosquitos. The 0.4% oil preparation mentioned above was diluted by a refined kerosene to 0.2%, and 0.3 ml. was sprayed. The results of the test for knock-down ratio of the common mosquitos are as follows.

a room at a constant temperature of 28 C. and the mortality was examined after hours.

Following are the results of the mortality of the house- Knock-down ratio of common mosquitos according to the lapse of time, percent 30 sec.

42 see.

1 min.

2 min.

1 min., 25 see.

2 min., 50 sec.

8 min.

5 min.,

min. sec.

The compound (1) The compound (II) Allethr'm 1 cue-no: cocoa kiwil 0.2% oil.

Example 24 Mortality (Percent) Concentration,

(Percent) 7 Oil solution of (III) 011 solution of (IV) Mortality (Percent) Concentration, (Percent) Emulsion of (V) Emulsion of (VI) Example 26 0.3 g. of phthalimidomethyl ester (VII) of chrysanthemum dicarboxylic acid was dissolved in 3 m1. of methylnaphthalene and, to this solution, a refined kerosene was added to make the total volume ml. Thus 0.3% oil solution was obtained.

In the same way as in Example 23, knock-down number of houseflies were examined. The results of the test were as follows:

Knock-down ratio of houseflies according to the lapse of time, percent 30 42 1 1 min., 2 2 min, 4 5 min., 8

sec. sec. min. 25 sec. min. 50 sec. min. 30 sec. min.

The compound (VII) 1.8 8.7 17 .1 26.5 32.4 41.3 50.1 51.8 55 .4 Allethrin 1 0 2 .6 9 .0 14 .2 27 .9 44 .3 54 .3 3 .5 78 .9

1 0.3 oil.

11 Example 27 Two grams of phthalirninomethyl ester of chrysanthemum monocarboxylic acid is dissolved in ml. of acetone, and the solution is mixed with 98 g. of 300 mesh (Taylor) talc. The mixture is well blended by a mixer, and the acetone is allowed to evaporate. Thus, a dust preparation containing 2% of the active ingredient is obtained.

Into a settling-tower attached with a cage in which about 30 houseflies (adult) are liberated, 100 mg. or 500 mg. of the dust preparation is scattered, and the houseflies are allowed to be exposed to the preparation as in Ex ample 25. After hours, the mortalities are observed.

Mg. Mortality, percent 1000 100.0

500 78.3 Control 2.5

What we claim is:

1. A composition comprising a carrier and as the essential ingredient an insecticidal amount of a cyclopropanecarboxylic acid ester having the formula,

R 0 X wherein X X X and X each means a member selected from the group consisting of hydrogen and halogen, methyl, nitro, methoxy, and cyano; Z is a member selected from the group consisting of oxygen and sulfur; Y is a member selected from the group consisting of a direct linkage and alkylene having carbon numbers of 1 to 3; and R is a member selected from the group consisting of methyl and methoxycarbonyl.

2. A composition comprising at least one hydrocarbon selected from the group consisting of methylnaphthalene, kerosene and xylene and as the essential ingredient an insecticidal amount of a cyclopropanecarboxylic acid ester having the formula,

Y Z N (1 CH3 on,

i 4 i wherein X X X and X each means a member selected from the group consisting of hydrogen and halogen, methyl, nitro, methoxy, and cyano; Z is a member selected from the group consisting of oxygen and sulfur; Y is a member selected from the group consisting of a direct linkage and alkylene having carbon numbers of 1 to 3; and R is a member selected from the group consisting of methyl and methoxycarbonyl.

3. A composition comprising an emulsifier and as the essential ingredient an insecticidal amount of a cyclopropanecarboxylic acid ester having the formula,

CH CH methyl, nitro, methoxy,'iand cyano; Z is a member se-' lected from the group consisting of oxygen and sulfur;

Y is a member selected trom the group consisting of a direct linkage and alkylene having carbon numbers of 1 to 3; and R is a member selected from the group consisting of methyl and methoxycarbonyl.

4. A composition comprising a powdered solid carrier and as the essential ingredient an insecticidal amount of a cyclopropanecarboxylic acid ester having the formula,

wherein X X X and X each means a member selected from the group consisting of hydrogen and halogen, methyl, nitro, methoxy, and cyano; Z is a member selected from the group consisting of oxygen and sulfur; Y is a member selected from the group consisting of a direct linkage and alkylene having carbon numbers of 1 to 3; and R is a member selected from the group consisting of methyl and methoxycarbonyl.

5. A composition comprising a carrier and as an essential ingredient an insecticidal amount of a cyclopropanecarboxylic acid ester having the formula,

wherein X X X and X each means a member selected from the group consisting of hydrogen and halogen, methyl, nitro, methoxy, and cyano; Z is a member selected from the group consisting of oxygen and sulfur; Y is a member selected from the group consisting of a direct linkage and alkylene having carbon numbers of 1 to 3; and R is a member selected from the group consisting of methyl and methoxycarbonyl, and, as another ingredient, 0,0-dimethyl-O-(3-methyl-4-nitrophenyl) thiophosphate, in ratio of 0.05:1 to 1:0.05 by weight of the ester to 0,0-dimethyl-O-(3-methyl-4-nitrophenyl) thiophosphate.

6. A method of killing insects which comprises contacting the insects with an insecticidal quantity of a cyclopropanecarboxylic acid ester having the formula,

wherein X X X and X each means a member selected from the group consisting of hydrogen and halogen, methyl, nitro, methoxy, and cyano; Z is a member selected from the group consisting of oxygen and sulfur; Y is a member selected from the group consisting of a direct linkage and alkylene having carbon numbers of 1 to 3; and R is a member selected from the group consisting of methyl and methoxycarbonyl.

References Cited by the Examiner UNITED STATES PATENTS 2,863,801 12/1958 Kuhle et a1 16733 2,884,355 4/1959 Goodhue et a1. 16733 3,060,191 10/1962 Kolb et a1 260326 3,064,006 11/ 1962 Novello 260326 JULIAN S. LEVITT, Primary Examiner.

VERA C. CLARKE, D. B. MOYER,

Assistant Examiners. 

6. A METHOD OF KILLING INSECTS WHICH COMPRISES CONTACTING THE INSECTS WITH AN INSECTICIDAL QUANTITY OF A CYCLOPROPANECARBOXYLIC ACID ESTER HAVING THE FORMULA, 